Hindered phenyl phosphites

ABSTRACT

Compounds of the formula ##STR1## wherein R 1  and R 2  are independently lower alkyl or hydrogen, provided that only one of R 1  and R 2  is hydrogen, 
     R 3  is --(A) g  --COOR 4  or CN where 
     A is alkylene of 1 to 6 carbon atoms, 
     R 4  is alkyl of 1 to 24 carbon atoms, phenyl or alkyl substituted phenyl, and 
     q is 0 or 1 are suitable for stabilizing organic material against thermal, oxidative and ultraviolet light degradation.

This is a divisional of application Ser. No. 710,063, filed on July 30,1976 now U.S. Pat. No. 4,094,855 which issued on June 13, 1978.

BACKGROUND OF THE INVENTION

The prior art discloses many materials which stabilize organic materialsagainst deterioration. For example, many varieties of compounds areknown which inhibit the discoloration of polymers on exposure to heatand light. Such protection is necessary because most organic polymers,especially polyolefins such as polyethylene or polypropylene, which areused for manufacturing articles tend to develop color with passage oftime. The discoloration may be due to various factors such as thedecomposition of the polymer, the antioxidant or to the presence ofresidual metal catalyst or residual peroxides used to controlpolymerization. It may also be due to the inherent nature of thepolymeric material, the additives used in the polymeric material or theeffect of heat on the polymeric material. The development of color isundesirable because it indicates polymer degradation and results infurther reduction of the quality of the polymer. Thus, one of theobjects of this invention is to provide a stabilized composition whichwould improve the quality of polymers by preventing the discoloration ofthe polymer.

Other unstable organic materials, such as synthetic lubricants,hydrocarbons, natural and synthetic rubbers, oils of animal or vegetableorigin, and the like are also unstable to thermal and/or oxidativedeterioration. Such materials may also be unstable to ultraviolet and/orvisible light.

It is well known to stabilize polyolefins and styrenic polymers by theuse of phosphites. Thus, for example, phosphites can be used inconjunction with UV absorbers such as benzophenones and benzotriazolesto achieve improved stabilization of polypropylene on outdoor exposureto sunlight. However, a phosphite is generally not used as the solelight stabilizer in polypropylene because of its limited effectiveness.Unexpectedly, it has been found that the phosphites of this inventioncan be used effectively in polymers, such as polypropylene, as the solelight stabilizer. Furthermore, some of the phosphites of this inventionact as antioxidants for polymers, both when used alone and incombination with thiosynergists.

DETAILED DISCLOSURE

This invention accordingly relates to hindered phenyl phosphites andorganic compositions stabilized therewith. More specifically, thesecompounds are useful as stabilizers of organic materials which aresubject to thermal, oxidative and ultraviolet light degradation. Thehindered phenyl phosphites of this invention have the formula ##STR2##wherein R₁ and R₂ are independently lower alkyl or hydrogen, providedthat only one of R₁ and R₂ is hydrogen,

R₃ is --(A)_(q) --COOR₄ or CN where

A is alkylene of 1 to 6 carbon atoms,

R₄ is alkyl of 1 to 24 carbon atoms, phenyl or alkyl substituted phenyl,

q is 0 or 1,

m and n are each 1 or 2, the values of m and n being such that thetrivalent state of P is satisfied,

R is

(a) halogen,

(b) hydroxyl, provided that m is 2 and n is 1 when R is hydroxyl,

(c) --XR₅ wherein X is S or O and R₅ is alkyl of 1 to 24 carbon atoms,phenyl, alkyl substituted phenyl, or when X is O is alkanoyl, benzoyl,or alkyl substituted benzoyl,

(d) a group of the formula ##STR3## wherein R₆ is phenylene, alkylsubstituted phenylene or alkylene, X is as defined above, and m and nare each 1,

(e) a group of the formula ##STR4## wherein R₇ is hydrocarbyldiacyl, R₁,R₂ and R₃ are as defined above, and m is 2 and n is 1,

(f) A group of the formula ##STR5## wherein R₁, R₂ and R₃ are as definedabove, and m and n are each 1.

R₁ and R₂ are independently lower alkyl having from 1 to 12, especially4 to 12, carbon atoms, or hydrogen, provided that only one of R₁ and R₂hydrogen. Preferably, one of R₁ and R₂ is a tertiary alkyl of 4 to 8carbon atoms. Most preferably, both R₁ and R₂ are tertiary alkyl of 4 to8 carbon atoms, as e.g., t-butyl.

Substituent R₃ is preferably --COOR₄, --CH₂ COOR₄, --(CH₂)₂ COOR₄ or CN.Substituent R₄ is preferably alkyl of 1 to 30 carbon atoms, especially 1to 24 carbon atoms, phenyl or phenyl substituted by 1 to 3 alkyl groupsof the formula ##STR6## in which R₈, R₉ and R₁₀ independently of oneanother are alkyl with 1 to 18 carbon atoms or hydrogen. Examples of R₄are methyl, ethyl, n-propyl, isopropyl, n-butyl, n-octyl, n-octadecyl,n-docosyl, and n-tetracosyl Examples of R₈, R₉ and R₁₀ are methyl,ethyl, iso-propyl, sec-butyl, tert-butyl, sec-amyl, tert-amyl,tert-hexyl, iso-octyl, tert-octyl, sec-nonyl, tert-nonyl, sec-dodecyl,tert-dodecyl, sec-tetradecyl, sec-hexadecyl, and octadecyl.

In preferred compounds of the invention having the substituent --XR₅, R₅is alkyl of 1 to 18 carbon atoms, phenyl, benzoyl, phenyl or benzoylsubstituted by 1 or 2 alkyl groups of 1 to 18, preferably 1 to 12 carbonatoms each, and alkanoyl having 1 to 30, more preferably 1 to 22 carbonatoms.

Examples of R₅ as alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl,octyl, dodecyl, octadecyl, and tetracosyl. Examples of R₅ as alkylsubstituted phenyl are methylphenyl, ethylphenyl, butylphenyl,octylphenyl, octadecylphenyl, dimethylphenyl, dibutylphenyl,dioctadecylphenyl. Examples of alkyl substituted benzoyl are4-tert-octyl-benzoyl, 4-tert-butyl-benzoyl, and 3,4-dimethylbenzoyl.Examples of R₅ as alkanoyl are acetyl, propionyl, butyroyl, pelargonyl,stearoyl, caproyl, capryloyl, 2-ethylhexanoyl, lauroyl, valeroyl,palmitoyl, tridecanoyl and octanoyl.

In preferred compounds of the formula ##STR7## the cyclic structure##STR8## is a 5 or 6 membered ring where R₆ is alkylene of 2 to 24,preferably 2 to 18, carbon atoms. Examples of R₆ are ethylene,trimethylene, 2,2-dimethyltrimethylene, hexadecylethylene, 1,2-phenyleneand alkyl substituted 1,2-phenylene where the alkyl group has 1 to 18carbon atoms.

In preferred compounds of the formula ##STR9## R₁₁ is alkylene of 1 to34 carbon atoms, arylene or the direct bond.

Examples of R₁₁ as alkylene are methylene, ethylene, propylene,trimethylene, tetramethylene, hexamethylene, octamethylene,decamethylene and octadecamethylene. Examples of R₇ as arylene are O-,m-, or p-phenylene, and 2,3-naphthylene.

As previously stated, the compounds of the present invention are usefulin the stabilization of organic material normally subject todeterioration. Organic materials such as, for example, the followingpolymers, can be stabilized using the compounds of the formula I.

1. Polymers which are derived from hydrocarbons with single or doubleunsaturation, such as polyolefins, for example, polyethylene, which canoptionally be crosslinked, polypropylene, polyisobutylene,polymethylbutene-1, polymethylpentene-1, polybutene-1, polyisoprene,polybutadiene, polystyrene, polyisobutylene, copolymers of the monomerson which the homopolymers mentioned are based, such as ethylenepropylenecopolymers, propylene-butene-1 copolymers, propylene-isobutylenecopolymers, styrene-butadiene copolymers and terpolymers of ethylene andpropylene with a diene, such as, for example, hexadiene,dicyclopentadiene or ethylidene-norbornene; mixtures of above mentionedhomopolymers, such as for example, mixtures of polypropylene andpolyethylene, polypropylene and polybutene-1, or polypropylene andpolyisobutylene.

2. Vinyl polymers containing halogen, such as polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, but also polychloropreneand chlorinated rubbers.

3. Polymers which are derived from α,β-unsaturated acids and theirderivatives, such as polyacrylates and polymethacrylates,polyacrylamides and polyacrylonitrile, as well as their copolymers withother vinyl compounds, such as acrylonitrile/butadiene/styrene,acrylonitrile/styrene and acrylonitrile/styrene/acrylic estercopolymers.

4. Polymers which are derived from unsaturated alcohols and amines ortheir acyl derivatives or acetals, such as polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate, polyallyl melamine and theircopolymers with other vinyl compounds, such as ethylene/vinyl acetatecopolymers.

5. Homopolymers and copolymers which are derived from epoxides, such aspolyethylene oxide or the polymers which are derived from bis-glycidylethers.

6. Polyacetals, such as polyoxymethylene and polyoxyethylene, as well asthose polyoxymethylenes which contain ethylene oxide as the comonomer.

7. Polyphenylene oxides.

8. Polyurethanes and polyureas.

9. Polycarbonates.

10. Polysulphones.

11. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 6, polyamide 6/6, polyamide6/10, polyamide 11 and polyamide 12.

12. Polyesters which are derived from dicarboxylic acids and dialcoholsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene glycol terephthalate or poly-14-dimethylol-cyclohexaneterephthalate.

13. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other, such asphenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

14. Alkyd resins, such as glycerine-phthalic acid resins and theirmixtures with melamine-formaldehyde resins.

15. Unsaturated polyester resins which are derived from copolymers ofsaturated and unsaturated dicarboxylic acids with polyhydric alcohols,with vinyl compounds as crosslinking agents, and also theirhalogen-containing modifications of low inflammability.

16. Natural polymers such as cellulose, rubber, proteins and theirpolymer-homologously chemically modified derivatives, such as celluloseacetates, cellulose proprionates and cellulose butyrates, or thecellulose ethers, such as methylcellulose.

17. High molecular monomeric substances, for example, mineral oils,animal and vegetable fats, oils and waxes, or oils, waxes and fats basedon synthetic esters.

The compounds of this invention are particularly useful as UV lightstabilizers, especially for the protection of polyolefins, for instance,polyethylene, polypropylene, poly(butene-1), poly(pentene-1),poly(3-methylbutene-1), poly(4-methylpentene-1), variousethylene-propylene copolymers and the like. The compounds of thisinvention are particularly useful in stabilizing polypropylene.

Other polymeric substrates in which the compounds of this invention areparticularly useful are polystyrene, including impact polystyrene, ABSresin, SBR, polyisoprene, as well as natural rubber, polyestersincluding polyethylene terephthalate and polybutylene terephthalate,including copolymers.

The compounds of this invention are also particularly useful instabilizing lubricating oils of various types including natural andsynthetic hydrocarbon lubricating oils, particularly paraffiniclubricating oils, aliphatic esters, polyalkylene oxides, silicones,esters of phosphoric and silicic acids, highly fluorine-substitutedhydrocarbons, and the like. Specifically, such aliphatic esters whichare usefully stabilized comprise dihexyl acetate,di-(2-ethylhexyl)acelate, di-(3,5,5-trimethylhexyl)glutarate,di(3,5,5-trimethylpentyl)glutarate, di-(2-ethylhexyl)pimelate,di-(2-ethylhexyl)adipate, diisoamyl adipate, triamyl tricarballylate,pentaerythritol tetracaproate, dipropylene glycol dipelargonate,1,5-pentanediol di-(2-ethylhexanoate), and the like. Other specificlubricants include polyisopropylene oxide, polyisopropylene oxidediether, polyisopropylene oxide diester, and the like, as well as methylsilicone, methylphenyl silicone, tetracosyl silicate, etc. andfluorinated oils, such as perfluorohydrocarbons.

The present invention also relates to the stabilization of fattymaterials, including oils of animal or vegetable origin, which tend todeteriorate on standing on exposure to atmospheric oxygen. Also withinthe scope of the invention are saturated and unsaturated hydrocarbonswhich tend to deteriorate on storage and use, such as for example,gasolines, jet fuels, diesel mineral oils, and the like. Suchhydrocarbons are protected against gum formation, discoloration andother deterioration with the stabilizers of the present invention.Greases and cutting oils may also be stabilized in the same fashion.

Fatty acids, such as stearic acid, cyclohexene and synthetic oils, suchas trimethylolpropane esters of acetic acid, n-valeric acid, hexanoicacid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid,2-ethylpropanoic acid, and 2-methylpentanoic acid, and mixtures thereofare also very effectively stabilized with the foregoing stabilizers.

As previously mentioned, the stabilizers of this invention are alsouseful in stabilizing rubber, e.g., artificial and natural rubber. Otherexamples of rubber which may be stabilized according to the inventioninclude polybutadiene rubber, polyisoprene rubber, styrene-butadienerubber, butyl rubber, nitrile rubber, neoprene rubber and blends ofartificial rubber with natural rubber, such as for example naturalrubber with polybutadiene rubber. Broadly contemplated is thestabilization of any rubber normally subject to degradation.

In general, the stabilizers of this invention are employed from about0.01 to about 5% by weight of the stabilized composition, although thiswill vary with the particular substrate and application. An advantageousrange is from about 0.05 to about 2%, and especially 0.1 to about 1%.

The compositions are prepared by a number of means, depending on thesubstrate. For example, the instant stabilizers can be mixed into liquidsubstrates and can be milled into thermoplastic substrates. For additionto varnishes, the stabilizers can be dissolved in a co-solvent and thisadded to the varnish. As mentioned hereinbefore and exemplifiedhereinafter, levels of the stabilizers in the substrate may varyconsiderably depending on the particular end application, degree ofprotection desired, variations in the substrate, and presence ofsynergizing stabilizers (ultraviolet absorbers, dialkylthiodipropionates, and the like).

Selecting the proper use level is well within the capabilities of thoseskilled in the art.

For addition to polymeric substrates, the stabilizers can be blendedbefore polymerization or after polymerization, during the usualprocessing operations, for example, by hot-milling, the composition thenbeing extruded, pressed, blow-molded or the like into films, fibers,filaments, hollow spheres and the like. The heat stabilizing propertiesof these compounds may advantageously stabilize the polymer againstdegradation during such processing at the high temperature generallyencountered. The stabilizers can also be dissolved in suitable solventsand sprayed on the surface of films, fabrics, filaments or the like toprovide effective stabilization. Where the polymer is prepared from aliquid monomer as in the case of styrene, the stabilizer may bedispersed or dissolved in the monomer prior to polymerization or curing.

In the case of crosslinked polyethylene, the compounds are added beforethe crosslinking.

The following may be mentioned as examples of further additives withwhich the compounds of the formula I can be co-employed:

1. Antioxidants

1.1 Simple 2,6-dialkylphenols, such as, for example,2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dioctadecyl-4-methylphenol.

1.2 Derivatives of alkylated hydroquinones, such as, for example,2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone,2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxy-anisole,3,5-di-tert-butyl-4-hydroxy-anisole,tris-(3,5-di-tert-butyl-4-hydroxyphenyl)-phosphite,3,5-di-tert-butyl-4-hydroxyphenyl stearate andbis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.3 Hydroxylated thiodiphenyl ethers, such as, for example,2,2'-thio-bis-(6-tert-butyl-4-methylphenol),2,2'-thio-bis-(4octylphenol),4,4'-thio-bis(6-tert-butyl-3-methylphenol),4,4'-thio-bis(3,6-di-sec-amylphenol),4,4'-thio-bis-(6-tert-butyl-2methylphenol) and4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl)-disulphide.

1.4 Alkylidene-bisphenols, such as, for example,2,2'-methylene-bis-(6-tert-butyl-4-methylphenol),2,2'-methylenebis-(6-tert-butyl-4-ethylphenol),4,4'-methylene-bis-(6-tert-butyl-2-methylphenol),4,4'-methylene-bis(2,6'-di-tert-butyl-phenol),2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol],1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-butane,1,1-bis(5-tert-butyl-4hydroxy-2-methylphenyl)-butane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)-propane,1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)-pentane andethylene glycol bis[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate].

1.5 O-, N- and S-benzyl compounds, such as, for example,3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic acid octadecyl ester,tris(3,5-di-tert-butyl-4-hydroxybenzyl)-amine andbis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthalate.

1.6 Hydroxybenzylated malonic esters, such as, for example,2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonic acid dioctadecylester, 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonic acid dioctadecylester, 2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic aciddidodecylmercaptoethyl-ester and2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic aciddi-[4-(1,1,3,3-tetramethylbutyl)-phenyl]-ester.

1.7 Hydroxybenzyl-aromatics, such as, for example,1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-di-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzeneand 2,4,6-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-phenol.

1.8 s-Triazine compounds, such as, for example,2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-s-triazine,2-octylmercapto-4,6-bis-(3,5-di-tert-butyl-4-hydroxy-anilino)-s-triazine,2-octylmercapto-4,6-bis-(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-s-triazine and1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate.

1.9 Amides of β-(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid suchas, for example,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl-hexahydro-s-triazineandN,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine.

1.10 Esters of β-(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid withmonohydric or polyhydric alcohols, such as, for example, methanol,ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, diethylene glycol, thiodiethylene glycol,neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol,trimethylhexanediol, trimethylolethane, trimethylolpropane,tris-hydroxyethyl isocyanurate and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

1.11 Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl propionic acidwith monohydric or polyhydric alcohols, such as, for example, methanol,ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol1,2-propanediol, diethylene glycol, thiodiethylene glycol,neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol,trimethylhexanediol, trimethylolethane, trimethylolpropane,tris-hydroxyethyl isocyanurate and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2,2,2]octane.

1.12 Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid withmonohydric or polyhydric alcohols, such as, for example, with methanol,ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol,trimethyl hexanediol, trimethylolethane, trimethylolpropane,tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha2,6,7-trioxabicyclo[2,2,2]octane.

1.13 Acylaminophenols, such as, for example,N-(3,5-di-tert-butyl-4-hydroxyphenyl)stearic acid amide,N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenyl)-thiobis-acetamide andthiophosphoric acid O,O-diethyl ester 3,5-di-tert-butyl-4-hydroxyanilide.

1.14 Benzylphosphonates, such as, for example,3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester,3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid diethyl ester,3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid dioctadecy ester and5-tert-butyl-4-hydroxy-3-methylbenzyl-phosphonic acid dioctadecyl ester.

1.15 Aminoaryl derivatives, such as, for example,phenyl-1-naphthylamine, phenyl-2-naphthylamine,N,N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine,N,N'-di-sec-butyl-p-phenylenediamine,6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline,6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, monooctyliminodibenzyland dioctyliminodibenzyl and polymerizes2,2,4-trimethyl-1,2-dihydroquinoline. Octylated diphenylamine, nonylateddiphenylamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine,N-phenyl-N'-isopropyl-p-phenylenediamine,N,N'-di-sec-octyl-p-phenylenediamine,N-phenyl-N'-sec-octyl-p-phenylenediamine,N,N'-di-(1,4-dimethylpentyl)-p-phenylenediamine,N,N'-dimethyl-N,N'-di-(sec-octyl)-p-phenylenediamine,2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec-butylaniline, thecondensation produced of diphenylamine and acetone,aldol-1-naphthylamine and phenothiazine.

2. UV absorbers and light stabilizers

2.1 2-(2'-Hydroxyphenyl)-benztriazoles, such as, for example, the5'-methyl-, 3'5'-di-tert.-butyl-, 5'-tert.butyl-,5'-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.-butyl-,5-chloro-3'-tert.-butyl-5'-methyl-, 3'-sec.-butyl-5'-tert.-butyl',3'-α-methylbenzyl-5'-methyl-, 3'-α-methylbenzyl-5'-methyl-5-chloro-,4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.-amyl-,3'-methyl-5'-carbomethoxyethyl- and5-chloro-3',5'-di-tert.-amyl-derivative.

2.2 2,4-Bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, such as, forexample, the 6-ethyl-, 6-heptadecyl-, or 6-undecylderivative.

2.3 2-Hydroxy-benzophenones, such as, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-,4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy-derivative.

2.4 1,3-Bis-(2'-hydroxy-benzoyl)-benzenes, such as for example,1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene,1,3-bis-(2'-hydroxy-4'-octyloxy-benzoyl)-benzene and1,3-bis-(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene.

2.5 Esters of optionally substituted benzoic acids, such as, forexample, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol,bis-(4-tert.-butylbenzoyl)-resorcinol, benzoyl-resorcinol and3,5-di-tert.-butyl-4-hydroxybenzoic acid 2,4-di-tert.-butyl-phenylester, octadecyl ester or 2-methyl-4,6-di-tert.-butyl-phenyl ester.

2.6 Acrylates, such as, for example, α-cyano-β, β-diphenylacrylic acidethyl ester or isooctyl ester, α-carbomethoxycinnamic acid methyl ester,α-cyano-β-methyl-p-methoxycinnamic acid methyl ester or butyl ester andN-(β-carbomethoxy-vinyl)-2methyl-indoline.

2.7 Nickel compounds, such as, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-di-ethanolamine, nickel complexes ofbis-[2-hydroxy-4-(1,1,3,3-tetramethylbutyl)-phenyl]-sulphone, such asthe 2:1 complex, optionally with additional ligands such as2-ethyl-caproic acid, nickel dibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketonoxime, nickel3,5-di-tert.-butyl-4-hydroxybenzoate and nickel isopropylxanthate.

2.8 Oxalic acid diamides, such as, for example,4,4'di-octyl-oxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert.-butyloxanilide,2,2'-di-dodecyloxy-5,5'-di-tert.-butyl-oxanilide2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert.-butyl-2'-ethyl-oxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert.-butyl-oxanilide and mixtures of ortho-and para-methoxy- as well as of o-and p-ethoxy-disubstituted oxanilides,

3. Metal deactivators, such as, for example, oxanilide, isophthalic aciddihydrazide, sebacic acid bis-phenylhydrazide, bis-benzylidene-oxalicacid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide,N,N'-bis-salicyloyloxalic acid dihydrazide,N,N'-bis-salicyloyl-hydrazine,N,N'-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hydrazine,N-salicyloyl-N'-salicylal-hydrazine, 3-salicyloylamino-1,2,4-triazoleand N,N'-bis-salicyloyl-thiopropionic acid dihydrazide.

4. Compounds which destroy peroxide, such as, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercapto-benzimidazole.

5. Polyamide stabilizers, such as, for example, copper salts incombination with iodides and/or phosphorus compounds and salts ofdivalent manganese.

6. Basic co-stabilizers, such as, for example, melamine, benzoquanamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acids,for example, Ca stearate, Zn searate, Mg stearate, Na ricinoleate and Kpalmitate, antimony pyrocatechloate or zinc pyrocatecholate.

7. PVC stabilizers, such as, for example, organic tin compounds, organiclead compounds and barium-cadmium salts of fatty acids.

8. Nucleating agents, such as, for example, 4-tert. butylbenzoic acid,adipic acid and diphenylacetic acid.

9. Urea derivatives, such as, for example,N-cyclohexyl-N'-1-naphthylurea, N-phenyl-N, N'-dicyclohexylura,N-phenyl-N'-2-naphthylurea, N-phenylthiourea and N,N'-dibutylthiourea.

10. Other additives, such as, for example, plasticizers, lubricants,emulsifiers, fillers, carbon black, asbestos, kaolin, talc, glassfibres, pigments, optical brighteners, flameproofing agents, antistaticagents, pourpoint depressants, corrosion and rust inhibitors, dispersingagents, demulsifiers, antifoaming agents, accelerators and the otherchemicals used in rubber compounding, antiozonants, dyes, pigments,metal chelating agents, dyesites and the like.

The hindered phosphites of this invention are particularly useful instabilizing polymer systems containing reinforcing agents and flameretardants, e.g., the compounds of this invention help to stabilizepolyesters, e.g., polybutylene terephthalate containing fiber glass andalso polyesters containing flame-retardants, e.g., polyethylene orpolybutylene terephthalate containing halogenated (e.g., brominated)aryl flame-retardants.

The hindered phosphites of this invention are particularly useful inpreventing discoloration due to processing as well as thermal aging andlight exposure of polymer compositions containing polyacrylonitrile andpolymethacrylonitrile resins. For example, a rubber modifiedpolyacrylonitrile used for beverage bottles is inhibited fromdiscoloration when a hindered phosphite of this invention is included inthe formulation.

Often combinations such as these, particularly the sulfur-containingesters (Section 4, page 24), and/or the ultraviolet light stabilizers(Section 2, pages 21-23), will produce superior results in certainapplications to those expected from the properties of the individualcomponents.

The following formula represents co-stabilizers which are in certaininstances very useful in combination with the stabilizers of thisinvention: ##STR10## wherein R₁₂ is an alkyl group having from 6 to 24carbon atoms, and n is an integer from 1 to 6. Especially usefulcompounds of this type are dilauryl-β-thiodipropionate (DLTDP),distearyl-β-thiodipropionate (DSTDP), and dimyristyl-β-thiodipropionate.The above co-stabilizers are used in the amount of from 0.005 to 5% byweight of the organic material, and preferably from 0.1 to 1%.

A useful co-stabilizer with which the stabilizers of this invention maybe combined has the formula ##STR11## wherein R₁₃ is hydrogen, chlorineor lower alkyl containing from 1 to 6 carbon atoms,

R₁₄ is hydrogen, alkyl containing 1 to 12 carbon atoms, phenyl orbenzyl, and

R₁₅ is hydrogen, chlorine or (lower) alkyl containing from 1 to 6 carbonatoms.

In a preferred embodiment, R₁₅ is hydrogen, chlorine or a methyl group;R₁₃ is hydrogen, chlorine, t-butyl, t-amyl; and R₁₄ is alkyl of from 1to 12 carbon atoms such as methyl, ethyl, hexyl, octyl, dodecyl,t-butyl, t-amyl, isopropyl and the like.

The above benzotriazoles are added to the polymer substrate in an amountof from about 0.005% to about 5% by weight based on the weight of thepolymer and more preferably from 0.05% to 2%.

Although the compounds of this invention are to some degree alsoeffective as thermal stabilizers, if the processing of the polymer iscarried out at high temperatures it is advantageous to incorporateadditional antioxidants.

In most applications, it is desirable to incorporate into the resincomposition, sufficient thermal antioxidants to protect the plasticagainst thermal and oxidative degradation. The amount of antioxidantrequired will be comparable to that of the actinic stabilizer. Namely,from about 0.005% to 5% and preferably from 0.01% to 2% by weight.

The best results have been obtained with the preferred class of thermalantioxidants, the hindered phenols. These compounds have been found toprovide the best thermal stabilization with the least discoloration inthe compositions of the invention. Among this preferred class of thermalantioxidants may be mentioned the following:

di-n-octadecyl(3,5-di-butyl-4-hydroxybenzyl)malonate

2,6-di-t-butylphenol

2,2'-methylene-bis(6-t-butyl-4-methylphenol)

2,6-di-t-butylhydroquinone

octadecyl-3(3,5-di-t-butyl-4-hydroxybenzylthio) acetate

1,1,3-tris-(3-t-butyl-6-methyl-4-hydroxyphenyl) butane

1,4-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene

2,4-bis-(3,5-di-t-butyl-4-hydroxyphenoxy)-6-(n-octyl-thio)-1,3,5-triazine

2,4-bis-(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octyl-thioethylthio)-1,3,5-triazine

2,4-bis-(n-octylthio)-6-(3,5-di-t-butyl-4-hydroxy-anilino)-1,3,5-triazine

2,4,6-tris-(4-hydroxy-3,5-di-t-butylphenoxy)-1,3,5-triazine

n-octadecyl-β-(3,5-di-t-butyl-4-hydroxyphenyl) propionate

2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate

di-n-dodecyl-6-tert-butyl-2,3-dimethyl-4-hydroxybenzyl phosphonate

stearamido N,N-bis-[ethylene3-(3,5,di-t-butyl-4-hydroxyphenyl)propionate]

1,2-propylene glycol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]

pentaerythritol tetrakis-[3,5-di-t-butyl-4-hydroxyphenyl)propionate]

dioctadecyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate

di-n-octadecyl 1-(3,5-di-t-butyl-4-hydroxyphenyl)ethanephosphonate

The above phenolic hydrocarbon stabilizers are known and many arecommercially available.

The above exemplified antioxidants and other related antioxidants whichare incorporated herein by reference, are disclosed in greater detail inthe following patents: Netherlands Pat. No. 67/1119, issued Feb. 19,1968; Netherlands Pat. No. 68/03498, issued Sept. 18, 1968; U.S. Pat.Nos. 3,255,191; 3,330,859; 3,644,482, 3,281,505; 3,531,483; 3,285,855;3,364,250; 3,368,997; 3,357,944 and 3,758,549.

In a particularly advantageous embodiment of the invention, the hinderedphosphites are employed in combination with p-hydroxybenzoates havingthe general formula ##STR12## wherein R₁₆ is (lower) alkyl containingfrom 1 to 6 carbon atoms,

R₁₇ is hydrogen or (lower) alkyl containing from 1 to 6 carbon atoms,and

R₁₈ is alkyl or alkenyl of from 1 to 24 carbon atoms, preferably alkylof from 1 to 24 carbon atoms, phenyl, lower alkyl substituted phenyl,benzyl or lower alkyl substituted benzyl groups, such that no more thantwo lower alkyl substituents are present on said phenyl or benzylgroups. Preferred among the above phenyl and benzyl groups defining R₁₈are phenyl and phenyl substituted by one or two alkyl groups of 1 to 12carbon atoms.

In a preferred embodiment, R₁₆ and R₁₇ are t-butyl or t-amyl groups andR₁₈ is a di(lower alkyl) phenyl. Illustrative examples ofhydroxybenzoates are given below:

(2',4'-di-t-butylphenyl)-3,5-di-t-butyl-4-hydroxybenzoate

methyl 3-methyl-5-isopropyl-4-hydroxybenzoate

ethyl 3,5-diisopropyl-4-hydroxybenzoate

propyl 3,5-di-sec-butyl-4-hydroxybenzoate

isobutyl 3,5-di-tert-amyl-4-hydroxybenzoate

decyl 3,5-di-tert-octyl-4-hydroxybenzoate

cyclohexyl 3,5-di-tert-amyl-4-hydroxybenzoate

dodecyl 3-methyl-5-isoamyl-4-hydroxybenzoate

octadecyl 3,5-diisopropyl-4-hydroxybenzoate

hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate

3-fluoropropyl 3,5-di-tert-amyl-4-hydroxybenzoate

allyl 3,5-di-tert-butyl-4-hydroxybenzoate

oleyl 5-methyl-5-tert-amyl-4-hydroxybenzoate

phenyl 3,5-diisopropyl-4-hydroxybenzoate

p-t-octylphenyl 3,5-di-tert-amyl-4-hydroxybenzoate

(2',4'-dimethylphenyl) 3,5-di-tert-octyl-4-hydroxybenzoate

p-isopropylphenyl 3-methyl-5-tert-amyl-4-hydroxybenzoate

naphthyl 3,5-di-tert-butyl-4-hydroxybenzoate

6-methylnaphthyl 3,5-di-tert-hexyl-4-hydroxybenzoate

p-chlorophenyl 3,5-di-tert-butyl-4-hydroxybenzoate

2,4-dibromophenyl 3,5-diisopropyl-4-hydroxybenzoate

The p-hydroxybenzoate light stabilizers of Formula II are added to thepolymer substrate in an amount of from about 0.005% to 5% by weightbased on the weight of polymer, and more preferably from 0.05% to 2%.

The compounds of this invention may be prepared by a number of methods.Method (1) can be represented by the following reaction path: ##STR13##where M is an alkali metal preferably sodium or potassium or hydrogenand Y is halogen preferably bromine or chlorine, more preferablychlorine, and the other symbols are as previously defined. Where M ishydrogen, a proton acceptor, preferably a tertiary amine, such astriethylamine, is used to neutralize the acid HY which is produced as aby-product.

Method (2), illustrated below, has been found particularly advantageousin producing compounds of this invention where m=2, n=1 and R=OH, byselective hydrolysis of compounds of this invention where m=2, n=1, and--XR₅ is alkanoyloxy, e.g., acetoxy, as shown in the following equation:##STR14## wherein R₁₉ is hydrogen or alkyl of 1 to 17 carbon atoms andthe other symbols are as previously defined. This novel method makespossible the synthesis of stabilizers not directly accessible from thephosphorochloridite (4).

Compound (2) above can be made as follows: ##STR15## where the symbolsare as previously defined.

Some of the compounds of this invention, tautomers 3 and 3a shown above,can also be made by hydrolysis or alcoholysis of the chlorodite as shownin method (3) below ##STR16## wherein R" is alkyl, preferably of 1 to 8carbon atoms, and the other symbols are as defined above.

The compounds of this invention of the formula ##STR17## where X is O orS and R₅ is alkyl, phenyl, or alkyl substituted phenyl and the othersymbols are as previously defined, can be made in known manner byreaction of a compound of the formula ##STR18## and the desired hydroxyor thiol compound, or the oxide or the thiolate.

The compounds of this invention of the formula ##STR19## can be made inknown manner by reaction of a compound of the formula ##STR20## and acompound of the formula ##STR21## where the symbols are as previouslydefined. Where M is hydrogen, a proton acceptor, preferably a tertiaryamine, such as triethylamine, is used to neutralize the acid HY which isproduced as a by-product.

The starting materials for making the compounds of the present inventionare available commercially and/or may readily be prepared by thoseskilled in the art from the teachings of the prior art.

The following examples, presented for illustration and not limitation,will further serve to typify the nature of the present invention. In theexamples, parts are by weight, unless otherwise indicated.

EXAMPLE 1 Bis-(2,6-di-tert-butyl-4-carbomethoxyphenyl)phosphorochloridite

27.48 grams of phosphorus trichloride was added dropwise at 24° to 30°C. over a period of 15 minutes to a solution of 105.6 grams of methyl3,5-di-tert-butyl-4-hydroxybenzoate and 40.4 grams of triethylamine in375 ml. of dry toluene. The turbid light-brown reaction mixture wasstirred at 75° to 80° C. for three hours. The precipitated triethylaminehydrochloride was filtered and the clear filtrate concentrated todryness at reduced pressure, the isolated residue being crystallizedfrom toluene yielding the desired product as colorless crystals meltingat 174°-176° C.

    ______________________________________                                        Analysis:                                                                               % C      % H        % Cl                                            ______________________________________                                        Calculated for                                                                 C.sub.32 H.sub.46 ClO.sub.6 P,                                                           64.78      7.82       5.98                                         M.W. - 593.13                                                                Found       64.68      7.53       5.58                                        ______________________________________                                    

EXAMPLE 2Bis-(2,6-di-tert-butyl-4-carbo-2'4'-di-tert-butyl-phenoxyphenyl)phosphorochloridite

The compound of this example was made by a similar procedure as theanalogous methyl ester (Example 1) by substituting2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate for methyl3,5-di-tert-butyl-4-hydroxybenzoate. The desired compound is isolated aswhite crystals melting at 212°-215° C.

    ______________________________________                                        Analysis:                                                                                  % C     % H       % Cl                                           ______________________________________                                        Calc. for C.sub.58 H.sub.82 ClO.sub.6 P                                                      73.97     8.77      3.76                                        M.W. - 941.67                                                                Found          74.17     8.49      4.13                                       ______________________________________                                    

EXAMPLE 3Bis-(2,6-di-tert-butyl-4-ethylcarbomethoxyphenyl)phosphorochloridite

20.5 grams of phosphorus trichloride was added dropwise at 30° to 38° C.over a period of 20 minutes to a solution of 87.6 grams of methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate in 117 grams oftriethylamine. The reaction mixture was then heated at reflux withstirring under nitrogen for 31/2 hours. 100 ml of benzene was added andheating at reflux continued for an additional 4 hours. The reactionmixture was diluted with about 300 ml of ether, washed twice with 300 mlportions of 3 N HCl and then washed thoroughly with water and finallydried over anhydrous sodium sulfate. After removal of drying agent byfiltration and solvent by distillation at reduced pressures, theisolated residue was crystallized successively from n-heptane andacetonitrile yielding the desired product as white crystals melting at93°-95° C.

    ______________________________________                                        Analysis:                                                                                  % C     % H       % Cl                                           ______________________________________                                        Calc. for C.sub.36 H.sub.54 ClO.sub.6 P                                                      66.61     8.39      5.46                                        M.W. - 649.23                                                                Found          66:37     8.40      5.77                                       ______________________________________                                    

EXAMPLE 4 4,4 Dimethyl-2,6-dioxaphosphite of 2,4-di-tert-butyl-phenyl3,5-di-tert-butyl-4-hydroxybenzoate

10.1 grams of triethylamine was added dropwise to a solution of 16.7grams of 4,4-dimethyl-2,6-dioxa-phosphorochloridite and 43.8 grams of2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate dissolved in200 ml methylene chloride at room temperature. The reaction mixture wasthen heated at reflux for 1 hour, cooled to room temperature, freed ofprecipitated triethylamine hydrochloride by filtration and finallyconcentrated to dryness by distillation of the solvent at reducedpressure. The residual solid was then crystallized from a solventmixture of hexane and toluene, yielding the desired product in the formof colorless crystals melting at 196°-197°.

EXAMPLE 5 Cyclic ethylene phosphite of 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate

10.12 grams was added dropwise at about 25° to 40° C. to a solution of12.6 grams of cyclic ethylene phosphorochloridite and 43.8 grams of2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate in 200 ml ofmethylene chloride. The reaction mixture was then heated at reflux fortwo hours, the precipitated triethylamine hydrochloride removed byfiltration and the crude product isolated as a solid after removal ofthe solvent by distillation at reduced pressure. The crude wascrystallized twice from toluene yielding the desired product ascolorless crystals melting at 155°-156° C.

    ______________________________________                                        Analysis:                                                                                  % C     % H       % P                                            ______________________________________                                        Calculated for C.sub.31 H.sub.47 O.sub.5 P                                                   70.40     8.58      5.86                                        M.W. - 530.67                                                                Found          70.66     8.89      5.69                                                      70.40     8.82                                                 ______________________________________                                    

EXAMPLE 6 Cyclic ethylene phosphite ofn-Octyl-3,5-di-tert-butyl-4-hydroxybenzoate

18.1 grams of n-octyl 3,5-di-tert-butyl-4-hydroxybenzoate and 6.3 gramsof cyclic ethylene phosphorochloridite and 5.0 grams of triethylamineare allowed to react together in 200 ml of methylene chloride whilebeing heated at reflux for 12 hours. After cooling the reaction mixtureto room temperature and washing twice with water, the organic phase wasdried over sodium sulfate. The organic solution was freed of dryingagent by filtration, concentrated to dryness by distillation of thesolvent at reduced pressure and the recovered oil crystallized frompentane. The desired product is thus obtained as white crystals meltingat 57°-58° C.

    ______________________________________                                        Analysis:                                                                                  % C     % H       % P                                            ______________________________________                                        Calculated for C.sub.25 H.sub.43 O.sub.5 P                                                   66.05     9.53      6.81                                        M.W. - 454.59                                                                Found          67.07     9.19      5.87                                       ______________________________________                                    

Mass spectra indicates that the title compound in contaminated with aminor amount of n-octyl 3,5-di-tert-butyl-4-hydroxybenzoate. Theconclusions are corroborated by IR and NMR spectra.

EXAMPLE 7 O-Acetyl-bis-(2,6-di-tert-butyl-4-carbomethoxyphenylester)phosphite

11.86 grams ofbis-(2,6-di-tert-butyl-4-carbomethoxyphenyl)phosphorochloridite(Example 1) was dissolved in 100 ml of anhydrous methanol containingsodium acetate and the resulting solution stirred for 3 hours at roomtemperature. The residue, obtained as a white solid after removal ofsolvent by distillation at 200 mm HG and finally at 1 mm Hg., was washedwith water, dried and crystallized from n-hexane. The desired productwas thus obtained as white crystals melting at 130°-133° C.

    ______________________________________                                        Analysis:                                                                                  % C     % H       % P                                            ______________________________________                                        Calc. for C.sub.34 H.sub.49 O.sub.8 P                                                        66.21     8.00      5.02                                        M.W. - 616.7                                                                 Found          66.04     7.80      4.95                                                                          5.00                                       ______________________________________                                    

EXAMPLE 8 Bis(2,6-di-tert-butyl-4-carbomethoxyphenyl ester)phosphoricacid

A solution of 10.5 grams ofO-acetyl-(2,6-di-tert-butyl-p-carbomethoxyphenyl ester)phosphite(Example 7) was dissolved in 100 ml of dioxane containing 9.0 grams ofwater and 1.0 gram of acetic acid and the materials heated together atreflux for 8 hours. After removal of the solvent at reduced pressures,the residue was crystallized successively from acetonitrile and ethylacetate yielding the desired product as white crystals melting at about211°-213° C.

    ______________________________________                                         Analysis:       % C         % H                                              ______________________________________                                        Calc. for C.sub.32 H.sub.47 O.sub.7 P                                                          66.81       8.26                                              M.W. - 574.7                                                                 Found            66.43       7.72                                             ______________________________________                                    

EXAMPLE 8A Bis(2,6-di-tert-butyl-4-carbomethoxyphenyl ester)phosphonicacid

6.0 grams of triethylamine dissolved in 100 ml of toluene are addeddropwise at 5° C. to 2.7 grams of phosphorus trichloride and 15.9 gramsof methyl-3,5-di-tertiary-butyl-4-hydroxybenzoate dissolved in 50 ml oftoluene and heated at reflux overnight. After cooling to roomtemperature and removing the triethylamine hydrochloride by filtration,the organic phase is washed three times with water, the separatedorganic solution is dried over sodium sulfate. After removal of theorganic solvent by distillation at reduced pressure; the isolatedresidue is crystallized from a hexane-toluene mixture yielding thedesired compound as white crystals M.P. 200°-201° C. contaminated byby-products.

EXAMPLE 9O-Acetyl-(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenyl)phosphite

The compound of this example (M.P. 174°-177° C.) is prepared by ananalogous method as that shown in Example 7 by substitutingbis-(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butyl-phenoxyphenyl)phosphorochloridite(Example 2) forbis-(2,6-di-tert-butyl-4-carbo-methoxyphenyl)phosphorochlorodite.

EXAMPLE 10Bis(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenylester)phosphonic acid

The compound of this example is prepared by an analogous method as thatdisclosed in Example 8 by hydrolyzing the title compound of Example 9except that p-toluenesulfonic acid is used as catalyst. The compound ofthis example has a melting point of 234°-237° C.

EXAMPLE 11O-Acetyl-(2,6-di-tert-butyl-4-ethyl-carbomethoxyphenyl)phosphite

The compound of this example (M.P. 123°-125° C.) is prepared by ananalogous method to that shown in Example 7 by substitutingbis(2,6-di-tert-butyl-4-carbomethoxyethylphenyl)phosphorochloridite(Example 3) forbis(2,6-di-tert-butyl-4-carbomethoxyphenyl)phosphorochlorodite.

EXAMPLE 12 Bis(2,6-di-tert-butyl-4-ethyl-carbomethoxyphenylester)phosphonic acid

The compound of this example is prepared by an analogous method to thatdisclosed in Example 8 by hydrolyzing the title compound of Example 11.The melting range observed is 105°-113° C. on crystallization fromm-heptane.

EXAMPLE 13

By essentially following the procedure of Example 1 and substituting thefollowing esters for methyl 3,5-di-tert-butyl-4-hydroxybenzoate:

(a) n-octadecyl 3-tert-butyl-4-hydroxybenzoate

(b) n-dodecyl 3-methyl-5-tert-butyl-4-hydroxybenzoate

(c) n-hexyl 3,5-di-isopropyl-4-hydroxybenzoate there are respectivelyobtained:

(a) bis-(2-tert-butyl-4-carbo-n-octadecyloxyphenyl)phosphorochloridite.

(b) bis-(2-methyl-5-tert-butyl-4-carbo-n-dodecyloxyphenyl)phosphorochloridite.

(c) bis-(2,6-di-isopropyl-4-carbo-n-hexoxyphenyl)phosphorochloridite.

EXAMPLE 14

By essentially following the procedure of Example 2 and substituting thefollowing esters for 2',4'-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate:

(a) 2'-methyl-4',6'-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate

(b) 2',6'-di-sec.-butyl-4'-methylphenyl3,5-di-tert-butyl-4-hydroxybenzoate

(c) 2',4',6'-tri-isopropylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate

(d) 2',4,6'-tri-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate

(e) 4'-n-dodecyl-2',6'-dimethylphenyl3,5-di-tert-butyl-4-hydroxybenzoate

there are respectively obtained:

(a)bis-(2,6-di-tert-butyl-4-carbo-2'-methyl-4',6'-di-tert-butylphenoxyphenyl)phosphorochloridite.

(b)bis-(2,6-di-tert-butyl-4-carbo-2',6'-di-sec.-butyl-4'-methylphenoxyphenyl)phosphorochloridite

(c)bis-(2,6-di-tert-butyl-4-carbo-2',4',6'-triisopropylphenoxyphenyl)phosphorochloridite

(d)bis-(2,6-di-tert-butyl-4-carbo-2',4',6'-tri-tert-butylphenoxyphenyl)phosphorochloridite.

(e)bis-(2,6-di-tert-butyl-4-carbo-2',6'-dimethyl-4'-n-dodecylphenoxyphenyl)phosphorochloridite.

EXAMPLE 15

By essentially following the procedure of Example 3 and substituting thefollowing esters formethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate:

(a) n-octadecyl 6-(3,5-di-tert-butyl-4-hydroxyphenyl)hexanoate.

(b) n-tetracosyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

(c) n-octyl 3,5-di-tert-butyl-4-hydroxyphenylacetate

there are respectively obtained:

(a)bis-(2,6-di-tert-butyl-4-n-pentyl-carbo-n-octadecyloxyphenyl)phosphorochloridite

(b)bis-(2,6-di-tert-butyl-4-ethyl-carbo-n-tetracosyloxyphenyl)phosphorochloridite

(c)bis-(2,6-di-tert-butyl-4-methyl-carbo-n-octyloxyphenyl)phosphorochloridite

EXAMPLE 16

By essentially following the procedure of Example 5 and substituting thefollowing phosphorochloridites for cyclic ethylene phosphorochloriditeof

(a) 2-Chloro-1,3,2-benzodithiaphosphole

(b) 2-Chloro-1,3,2-benzodioxaphosphole

(c) ethylene phosphorochloridothioate

there are obtained the corresponding cyclic phosphites of2,4-di-tert-butyl 3,5-di-tert-butyl-4-hydroxybenzoate.

EXAMPLE 16A

In a similar manner to Example 16 there are obtained the correspondingcyclic phosphites by reaction of each of

(a) cyclic ethylene ester of phosphorochloridous acid

and

(b) cyclic 2,2-dimethyltrimethylene ester of phosphorochloridous acidwith each of the following:

(c) methyl 3,5-di-tert-butyl-4-hydroxybenzoate

(d) octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate

(e) methyl 3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)phosphonate

(f) n-octyl (3,5-di-tert-butyl-4-hydroxyphenyl)acetate

(g) n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate

EXAMPLE 17

By essentially following the procedure of Example 7 and substituting thefollowing salts for sodium acetate:

(a) sodium benzoate

(b) sodium propionate

(c) sodium stearate

there are respectively obtained:

(a) O-benzoyl-bis(2,6-di-tert-butyl-p-carbomethoxyphenyl)phosphite

(b) O-propionyl-bis(2,6-di-tert-butyl-p-carbomethoxyphenyl)phosphite

(c) O-stearyl-bis(2,6-di-tert-butyl-p-carbomethoxyphenyl)phosphite

EXAMPLE 18Bis-(2,6-di-tert-butyl-4-carbo-n-octadecyloxyphenyl)phosphorochloridite

The compound of this example was made in a similar manner to that ofExample 1 by reacting phosphorus trichloride withn-octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate employing triethylamineas acid acceptor. The product was isolated as a waxy white solid.

    ______________________________________                                        Analysis:                                                                                    % Cl                                                           ______________________________________                                        Calc.            3.31                                                         Found            2.82                                                         ______________________________________                                    

EXAMPLE 19O-Acetyl-bis(2,6-di-tert-butyl-4-carbo-n-octadecyloxyphenyl)phosphite

The compound of this example was made in a similar manner to that ofExample 7 by reacting the compound of Example 18 with sodium acetatedissolved in a solvent mixture of methanol and benzene. The compound ofthis example melts at 70°-75° C. after successive crystallization fromethyl acetate and isopropanol.

EXAMPLE 20 Bis(2,6-di-tert-butyl-4-carbo-n-octadecyloxyphenylester)phosphonic acid

The compound of this example was made in a similar manner to that ofExample 8 by hydrolyzing the compound of Example 19 in a water-dioxanemedium at reflux (95°-96° C.) in the presence of a catalytic amount ofp-toluenesulfonic acid. The compound of this example is isolated aswhite crystals melting at 114°-116° after crystallization from methylethyl ketone.

    ______________________________________                                        Analysis:                                                                                    % C       % H                                                  ______________________________________                                        Calc.            75.38       11.02                                            Found            75.17       11.14                                            ______________________________________                                    

EXAMPLE 21Bis-(2,6-di-tert-butyl-4-ethylcarbo-n-octadecyloxyphenyl)phosphorochloridit

The compound of this example was made in a similar manner to that ofExample 3 by reacting n-octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate with phosphorustrichloride in triethylamine. The product was isolated as a white waxysolid. Infrared absorption spectrum conformed to the structure of thisproduct.

EXAMPLE 22O-Acetyl-bis(2,6-di-tert-butyl-4-ethylcarbo-n-octadecyloxyphenyl)phosphite

A. The compound of this example (M.P. 44°-47°) was prepared by ananalogous method to that disclosed in Example 7 by reacting the compoundof Example 21 with sodium acetate dissolved in methanol.

B. By following the above procedure (A) and employing the appropriatephosphorochlorite starting compounds the following compounds areprepared:

(a) O-acetyl-bis(2-tert-butyl-4-carbo-n-octadecyloxyphenyl)phosphite

(b) O-acetyl-bis(2,6-di-isopropyl-4-carbo-n-hexoxyphenyl)phosphite

(c)O-acetyl-bis(2,6-di-tert-butyl-4-carbo-2',4',6'-tri-isopropylphenoxyphenyl)phosphite

(d)O-acetyl-bis(2,6-di-tert-butyl-4-carbo-2',4',6'-tri-tert-butylphenoxyphenyl)phosphite

(e)O-acetyl-bis(2,6-di-tert-butyl-4-n-pentyl-carbo-n-octadecyloxyphenyl)phosphite

(f)O-acetyl-bis(2,6-di-tert-butyl-4-methyl-carbo-n-octyloxyphenyl)phosphite

EXAMPLE 23 Bis(2,6-di-tert-butyl-4-ethylcarbo-n-octadecyloxyphenylester)phosphonic acid

A. The compound of this example was prepared by an analogous method tothat disclosed in Example 8 by hydrolyzing the compound of Example 22 inaqueous dioxane at reflux (Ca. 96°) using p-toluene sulfonic acid ascatalyst. The compound melts at 72°-75° C. after being purified bydry-column chromotography using silica-gel.

    ______________________________________                                        Analysis:                                                                                    % C       % H                                                  ______________________________________                                        Calc.            75.90       11.19                                            Found            75.87       10.88                                            ______________________________________                                    

B. By following the above procedure (A) and employing the appropriateo-acetyl bis-phosphite starting compounds listed in Example 22(B) thefollowing compounds are prepared:

(a) bis(2-tert-butyl-4-carbo-n-octadecyloxyphenyl ester)phosphonic acid

(b) bis(2,6-di-isopropyl-4-carbo-n-hexoxyphenyl ester)phosphonic acid

(c) bis(2,6-di-tert-butyl-4-carbo-2',4',6'-tri-isopropylphenoxyphenylester)phosphonic acid

(d) bis(2,6-di-tert-butyl-4-carbo-2',4',6'-tri-tert-butylphenoxyphenylester)phosphonic acid

(e) bis(2,6-di-tert-butyl-4-n-pentyl-carbo-n-octadecyloxyphenylester)phosphonic acid

(f) bis(2,6-di-tert-butyl-4-methyl-carbo-n-octyloxyphenylester)phosphonic acid.

EXAMPLE 24

1,000 parts of polypropylene powder (Moplen Fiber Grade) powder [meltindex 20 (230° C., 2,160 g)] are mixed in a Brabender kneader at 200° C.with 2 parts of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acidoctadecyl ester and 2.5 parts of the light stabilizer of the invention.

The mixture homogenised in this way is withdrawn from the kneader and ispre-pressed, by means of a toggle press, into sheets 2-3 mm thick whichare then converted at 260° C. in a heated platen press by means ofsuitable matrices, first into films 0.3 mm thick and, in a furtherprocess step, into films 0.1 mm thick.

The films thus produced are heat-treated for 1 hour at 150° C., whileavoiding cooling below 150° C., and, directly afterwards, are chilled inwater at 15° C. The films produced in this way have a homogeneousstructure of fine spherulites. Test pieces punched from them have anelongation of approx. 800%.

The films without light stabilizer which were used as a comparison areproduced in the same manner.

The polypropylene films are mounted on sample carriers and exposed in aXeno-150 testing apparatus. After varying periods of time, pieces offilm are with drawn, 5 test pieces are punched from each in the form oftensile test bars and the residual elongation of the latter isdetermined. The time of exposure, after which the elongation at break ofthe films has declined to 50% of its value before exposure, is taken asa measure of the protective action of the light stabilizer. The valueobtained are listed in the tables which follow

                  Table Ia                                                        ______________________________________                                        LIGHT STABILIZATION DATA IN POLYPROPYLENE                                                       Hours of exposure in the                                                      Xeno apparatus when the                                                       elongation at break has                                                       declined to 50% of the                                      Stabilizer*       initial value                                               ______________________________________                                        cyclic ethylene phosphite of                                                  2,4-di-tert-butylphenyl 3,5-                                                  di-tert-butyl-4-hydroxybenzoate                                                                 4310                                                        4,4-dimethyl-2,6-dioxaphosphite                                               of 2,4-di-tert-butylphenyl-3,5-                                               di-tert-butyl-4-hydroxybenzoate                                                                 2560                                                        None              800                                                         ______________________________________                                         *0.25% of the indicated stabilizer is present in the above formulations.      Each formulation and the blank also contain 0.2% octadecyl                    3(3',5di-t-butyl-4hydroxyphenol)propionate.                              

                  Table Ib                                                        ______________________________________                                                          Hours of exposure in the                                                      Xeno apparatus when the                                                       elongation at break has                                                       declined to 50% of the                                      Stabilizer*       initial value                                               ______________________________________                                        cyclic ethylene phosphite of                                                  n-octyl 3,5-di-tert-butyl-4-                                                  hydroxybenzoate   4340                                                        bis(2,6-di-tert-butyl-p-                                                      carbomethoxy phenyl ester)                                                    phosphonic acid   5198                                                        None              1040                                                        ______________________________________                                         *0.25% of the indicated stabilizer is present in the above formulations.      Each formulation and the blank also contain 0.2% octadecyl                    3(3',5di-t-butyl-4hydroxyphenol)propionate.                              

Comparatively good stabilization is obtained when the concentration ofhindered phosphite varies from 0.05% to 1%.

Other hindered phenolic antioxidants may be used in place of octadecyl3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate in the above mentionedcompositions with hindered phosphites as, for example, di-n-octadecylα-(3-t-butyl-4-hydroxy-4-methylbenzyl)malonate,2,4-bis(n-octylthio)-6-(3,4-di-t-butyl-4-hydroxyaniline)-1,3,5-triazine,tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane,di-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate,tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate,26,-di-tert-butyl-4-methylphenol,N,N,N-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-trimethylbenzene.

The hindered phosphite compositions of the above tables are alsostabilized when the following UV absorbers are added to thecompositions:

(a) 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate

(b) 2-hydroxy-4-n-octoxybenzophenone

(c) 2,2'-thiobis(4-t-octylphenolate)-1-n-butylamine nickel II

(d) p-octylphenyl salicylate

(e) 2,2'-dihydroxy-4,4'-dimethoxybenzophenone

(f) 2(2'-hydroxy-5'-methylphenyl)-benzotriazole

(g) 2(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole.

The compositions of the above tables are also stabilized when theindicated phosphites are replaced with the following stabilizers:

(a) O-acetyl-bis-(2,6-di-tert-butyl-4-carbomethoxyphenyl ester)phosphite

(b) bis(2,6-di-tert-butyl-4-carbomethoxyphenyl ester)phosphonic acid

(c) bis(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenylester)phosphonic acid

(d)O-acetyl-(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenyl)phosphite

(e) bis(2,6-di-tert-butyl-4-ethyl-carbomethoxyphenyl ester)phosphonicacid

(f) bis-(2,6-di-tert-butyl-4-carbomethoxyphenyl) phosphorochloridite

(g) O-acetyl-(2,6-di-tert-butyl-4-ethylcarbomethoxyphenyl)phosphite

(h) bis-(2,6-di-tert-butyl-4-carbo-n-octadecyloxyphenyl ester)phosphonicacid

(i) bis-(2,6-di-tert-butyl-4-ethylcarbo-n-octadecyloxyphenylester)phosphonic acid.

EXAMPLE 25

High impact polystyrene resin containing elastomer (i.e.,butadiene-styrene) is stabilized against loss of elongation propertiesdue to exposure to ultraviolet light by incorporation of 0.2% by weightof 4,4-dimethyl-2,6-dioxaphosphite of 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

The unstabilized resin is dissolved in chloroform and the stabilizerthen added, after which the mixture is cast on a glass plate and thesolvent evaporated to yield a uniform film which, upon drying, isremoved and cut up, and then pressed for 7 minutes at a temperature of163° C. and a pressure of 2,000 pounds per square inch into sheet ofuniform thickness (25 mil). The sheets are then cut into stripsapproximately 4×0.5 inches. A portion of these strips is then measuredfor percent of elongation in the Instron Tensile Testing Apparatus(Instron Engineering Corporation, Quincy, Mass.). The remaining portionsof the strips are placed in an FS/BL chamber where the samples aremounted on white cardboard stock and the time to 50% reduction inelongation is measured. The stabilized polystyrene resin retains itselongation property longer than the unstabilized resin.

EXAMPLE 26

Unstabilized linear polyethylene is solvent blended in methylenechloride with 0.5% by weight of the substrate ofO-acetyl-bis(2,6-di-tert-butyl-p-carbomethoxyphenyl ester)phosphite andthen vacuum dried. The resin is then extrusion compounded on a 1 inch24/1=L/D extruder, melt temperature 450° F. (232° C.) and pressed for 7minutes at a temperature of 163° C. and a pressure of 2,000 psi into asheet of uniform thickness of 100 ml. The sheets are then cut intoplaques of 2 inch×2 inch. The plaques are then exposed in an FS/BLexposure device and color measurements made periodically using a HunterColor Difference Meter Model D25. Polyethylene stabilized with the abovecompound is found to be much more stable than the unstabilizedpolyethylene or the polyethylene stabilized only with an antioxidant.

EXAMPLE 27

A quantity of SBR emulsion containing 100 g of rubber (500 ml of 20% SBRobtained from Texas U.S., Synpol 1500) previously stored under nitrogen,is placed in a beaker and stirred vigorously. The pH of the emulsion isadjusted to 10.5 with a 0.5 N NaOH solution.

To the emulsion is added 50 ml of 25% NaCL solution. A 6% NaCl solutionadjusted with hydrochloric acid to pH 1.5 is added in a thin stream withvigorous stirring. When pH 6.5 is reached, the rubber begins tocoagulate and the addition is slowed down in order to maintain uniformagitation. The addition of the acidic 6% NaCl solution is terminatedwhen a pH 3.5 is reached. The coagulated crumb-rubber slurry at pH 3.5is stirred for 1/2 hour.

The coagulated rubber is isolated by filtration through cheese cloth,and rinsed with distilled water. After three subsequent washings withfresh distilled water, the coagulated rubber is dried, first at 25 mm Hgand finally to constant weight under high vacuum (>1 mm) at 40°-45° C.

The dried rubber (25 g) is heated under nitrogen at 125° C. in aBrabender mixer and to this is added with mixing 0.25 g (0.5%) of thecyclic ethylene phosphite of 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate. The composition is mixed for 5minutes after which it is cooled and compression molded at 125° C. into5"×0.025" plaques.

The plaques are exposed to an Xenon Arc weatherometer and the colormeasurement (L-b) is made after 45, 125 and 290 hours. The samplesstabilized with the above compound are found to be much more lightstable than the unstabilized samples.

EXAMPLE 28

Unstabilized thoroughly dried polyethylene terphthalate chips are dryblended with 1.0% of bis(2,6-di-tert-butyl-p-carbomethoxyphenyl ester)phosphonic acid. 60/10 denier multifilament is melt spun at a melttemperature of 290° C. The oriented fiber is wound on white cards andexposed in an Xenon Arc Fadeometer. Color measurements are madeperiodically with a Hunter Color Difference Meter Model D25. Thestabilized samples are found to be much more light stable than theunstabilized samples.

EXAMPLE 29

(a) A composition comprising acrylonitrilebutadiene-styrene terpolymerand 1% by weight ofbis(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenylester)phosphonic acid resists embrittlement due to exposure toultraviolet light longer than one which does not contain the stabilizer.

(b) A composition comprising polyurethane prepared from toluenediisocyanate and alkylene polyols and 1.0% by weight ofO-acetyl-(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenyl)phosphiteis more stable to sunlight, fluorescent sunlamps, black lights andfluorescent lights than the unformulated polyurethane.

(c) A composition comprising a polycarbonate prepared from bisphenol-Aand phosgene and 1% by weight ofbis(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenylester)phosphonic acid resists discoloration due to exposure toultraviolet light longer than one which does not contain the stabilizer.

(d) A composition comprising polymethylmethacrylate and 0.25% by weightof bis(2,6-di-tert-butyl-4-carbo-2',4'-di-tert-butylphenoxyphenylester)phosphonic acid resists discoloration due to exposure toultraviolet light longer than one which does not contain the stabilizer.

EXAMPLE 30

(a) A stabilized polyamide (nylon 6,6) is prepared by incorporatingtherein 0.1% of bis(2,6-di-tert-butyl-p-carbomethoxyphenylester)phosphonic acid. The light stability of the stabilized compositionis superior to that of an unstabilized polyamide.

(b) A stabilized polyphenylene oxide polymer (prepared by polymerizing2,6-dimethylphenol is prepared by incorporating therein 0.5% by weightof the cyclic ethylene phosphite ofn-octyl-3,5-di-tert-butyl-4-hydroxybenzoate. The stabilized compositionsresist embrittlement due to exposure to ultraviolet light longer thanone which does not contain the stabilizer.

(c) A stabilized crystalline polystyrene is prepared by incorporatingtherein 0.1% weight of the cyclic ethylene phosphite of3,5-di-tert-butyl-4-hydroxybenzonitrile. The stabilized compositionresists embrittlement due to exposure to ultraviolet light longer thanone which does not contain the stabilizer.

Antioxidants may also be incorporated into each of the above mentionedcompositions, for example,di-n-octadecyl-α,α'-bis(3-t-butyl-4-hydroxy-5-methylbenzyl) malonate,2,4-bis(4-hydroxy-3,5-di-t-butylphenoxy)-6-(n-octylthioethylthio)-1,3,5-triazine,2,4-bis(3,5-di-t-butyl-hydroxyphenoxy)-6-(n-octylthio-1,3,5-triazine,di-n-octadecyl 3(3',5'-di-t-butyl-4-hydroxyphenyl)propionate,respectively.

EXAMPLE 31 Method of Testing Antioxidants in Polypropylene

Unstabilized polypropylene powder (Hercules Profax 6501) was thoroughlyblended with the indicated amounts of additives. The blended materialswere then milled on a two-roll mill at 182° C. for 5 minutes, afterwhich time the stabilized polypropylene was sheeted from the mill andallowed to cool.

The milled polypropylene sheets were then cut into pieces andcompression molded on a hydraulic press at 220° C., 175 psi into 25 milthick plaques.

Testing Method: Rotary Oven-Aging Test

The resulting plaques of 25 mil thickness were tested for resistance toaccelerated aging in a rotary oven at 150° C. When the plaques showedthe first signs of decomposition (e.g., cracking or brown edges) theywere considered to have failed. The results are shown below in thetable. The amounts of the additives are expressed in weight percentbased on the weight of the polymer.

                  TABLE 2                                                         ______________________________________                                        Stabilizing Effectiveness of Bis-(2,6-di-                                     tert-butyl-4-ethylcarbo-n-octadecyloxyphenyl                                  ester)phosphonic acid (Ex. 23) in Polypropylene 6501                                                Time to                                                                       Failure                                                 Formulations          Hrs.                                                    ______________________________________                                        Blank                  3                                                      0.3% Bis-(2,6-di-tert-butyl-4-                                                ethylcarbo-n-octadecyloxyphenyl                                               ester)phosphonic acid 250                                                     0.3% DSTDP            100                                                     0.1% (Bis-(2,6-di-tert-butyl-4-                                               ethylcarbo-n-octadecyloxyphenyl                                               ester)phosphonic acid + 0.3% DSTDP                                                                  400                                                     ______________________________________                                    

The results of Table show that the compound is an effective antioxidantfor polypropylene alone and with distearylthiodipropionate (DSTDP).

What is claimed is:
 1. A compound of the formula ##STR22## wherein R₁and R₂ are independently lower alkyl or hydrogen, provided that only oneof R₁ and R₂ is hydrogen,R₃ is --(A)--COOR₄ or CN where A is alkylene of1 to 3 carbon atoms, R₄ is alkyl of 1 to 24 carbon atoms, phenyl oralkyl substituted phenyl, and R is 0 or
 1. 2. A composition of mattercomprising an organic polymeric synthetic material normally subject tothermal, oxidative and ultraviolet degradation stabilized with(a) 0.005%to 5% of a stabilizing compound according to claim 1; (b) 0 to 5% of aphenolic antioxidant, (c) 0 to 5% of a thio co-stabilizer, (d) 0 to 5%of a UV absorber, and (e) 0 to 5% of a light stabilizer.
 3. A compoundaccording to claim 1 wherein R₁ and R₂ are independently alkyl having 4to 12 carbon atoms, R₃ is a group selected from --COOR₄, --CH₂ COOR₄,--(CH₂)₂ COOR₄ or --CN, R₄ is alkyl of 1 to 24 carbon atoms, phenyl orphenyl substituted by 1 to 3 alkyl groups each having 1 to 18 carbonatoms, and R, m and n are as defined in claim
 1. 4. A compound accordingto claim 3 wherein R₁ and R₂ are tert-butyl groups and R is hydroxyl. 5.A compound according to claim 3 of the formula ##STR23## wherein R₁ andR₂ are tert-butyl groups and R₃ is as defined in claim
 2. 6. Acomposition according to claim 2 wherein the organic material is apolyolefin.
 7. A composition according to claim 2 wherein the organicmaterial is polypropylene.
 8. A composition according to claim 2 whereinthe stabilizing compound (a) is the sole light stabilizer, theconcentrations of the UV absorber of (d) and the light stabilizer of (e)being equal to
 0. 9. A composition according to claim 2 consistingessentially of(i) polyolefin, (ii) a stabilizing compound (a), and (iii)0.005 to 5% of a phenolic antioxidant selected from tetrakis methane,octadecyl 3-[3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate,di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate,2,6-di-t-butyl-4-methylphenol, andtris-2,4,6-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate.
 10. Acomposition according to claim 2 wherein the stabilizing compound (a) isthe sole antioxidant and where (b) is equal to 0.